Water-soluble liquid detergent compositions



United States Patent 3,190,336 WATER-SQLUBLE LEQUED DETERGENT CGMPUSHTIGNS Robert C Taylor, King at Prussia, and Elizabeth .i. Meehan, Fort Washington, Pan, assignors to The Atlantic Refining Company, Philadelphia, Pa., a

corporation of Pennsylvania No Drawing. Filed July 3, 1962, fier. No. 207,410

, 6 Claims. (Cl. 252-453) This invention relates to water-solubleliquid detergent compositions and more particularly to water-soluble liquid detergent compositions containing a mixture of an anionic surface-active agent and a nonionic surface-active agent.

In recent years, a demand has arisen for a so-called all-purpose liquid detergent which can be used either in its concentrated form or diluted with water. Such a detergent may be sold in its concentrated form for use in cleaning oil and grease from various surfaces such as painted surfaces, floors, walls and the like; or the concentrated detergent may be sold to a distributor for dilution with water to be re-sold as a household cleaner for lighter duty. Since both the concentrated detergent and the diluted detergent must have a satisfactory shelf life, it is necessary that the concentrated liquid detergent remain in the form of a homogeneous solution Without separation into two phases on standing, and that when admixed With from 3 to 4 volumes of water it forms a homogeneous solution which, on standing for weeks or months, does not separate into two phases.

If either the concentrated liquid detergent or the diluted detergent is to be used by the consumer in the form of a more highly diluted aqueous solution, it is, of course, less critical that the detergent be completely water-soluble at these high dilutions, since such solutions will ordinarily be used immediately and agitated during use, thereby assuring a relatively completely homogeneous solution or dispersion.

Accordingly, the criteria for an all-purpose liquid detergent are that in concentrated form it is homogeneous and remains so on standing and likewise when diluted with from 3 to4 volumes of water it forms a homogeneous, stable solution which does not separate on standing. In addition, of course, such detergents also must be highly efiicient for removing oil, grease and stains from floors, walls, Woodwork, and similar hard surfaces.

A composition now has been found which consists of a mixture of an anionic surface-active agent and a nonionic surface-active agent dissolved in a solvent, which composition is a clear, homogeneous, non-separating solution and which, when admixed with from 3 to 4- volumes of water, also gives a homogeneous non-separating solution.

It is ariobject of this invention to provide a water-soluble liquid detergent composition which is homogeneous and does not separate on standing.

It is another object of this invention to provide a liquid detergent composition which,- when admixed with from 3 to 4 volumes of water, forms a homogeneous, non-separating solution.

It is a further object of this invention to provide a liquid detergent composition consisting of a mixture of an anionic surface-active agent and a nonionic surfaceactive agent in a solvent for use in. cleaning hard surfaces.

Other objects of this invention will be apparent from the detailed description of the invention and the claims that follow.

In accordance with this invention, a concentrated liquid detergent composition is compounded from about 50 weight percent to 60 weight percent of a mixture consisting of from about weight percent to weight percent of an anionic surface-active agent and from about weight percent to 50 weight percent of a nonionic surtions and solutions.

$190,836 Patented June 22, 1965 ice face-active agent with the remainder of the detergent composition consisting of a solvent. The anionic surface-active agent which is utilized to produce the com position of this invention consists of the triethanolamine salt of a C C alkyl benzene sulfonic acid, wherein the alkyl group averages about 12 carbon atoms, in theform of an aqueous solution containing about 60 weight percent of the triethanolamine sulfonate. One such commerical product is sold under the trade name Ultrawet 60L. It is made by polymerizing propylene to the tetramer using a phosphoric acid-on-kieselguhr catalyst, alkylating benzene with the propylene tetramer using an aluminum chloride catalyst, fractionating to obtain a C -C alkylated benzene with the average being about 12 carbon atoms in the alkyl group, sulfonating the alkylated benzene using 20 percent oleurn and finally neutralizing the sulfonic acid with triethanolamine.

The nonionic surface-active agent, which is admixed with the anionic surface-active agent, consists of a socalled alkyl aryl polyether alcohol, i.e., the condensation product of an alkyl phenol with ethylene oxide. The nonionic surface-active agent for use in this invention is the product obtained by condensing 5 moles of ethylene oxide with one mole of an octyl phenol. The condensation products have the structural formula wherein R is a C alkyl (octyl) group and x averages 5.

This condensation product is available commercially cent of the. mixture of surface-active agents.

It has been found necessary, in order to obtain the clear, liquid detergent compositions which also .can be diluted with water to produce non-separating solutions in accordance with this invention, to utilize the triethanolamine salt rather than the sodium'salt or other metal salts of the alkyl benzene sulfonic acid.

Likewise, it has been found that the described octyl phenol-ethylene oxide condensation product is required to produce the desired clear and homogeneous composi- Thus, the balance between the solubility properties of the anionic surface-active agent and the solubility proper-ties of the nonionic surfaceactive agent is exceedingly critical in order to obtain a water-soluble, clear, homogeneous, non-separating solution.

The solvent employed for the remainder of the cornpositi-on may be entirely aromatic, for example, it may be a C C alkyl benzene having an average of about 12 carbon atoms in the alkyl group or it may be a hydrocarbon mixture, for example, a petroleum hydrocarbon distillate fraction boiling between about 175 F. and 600 F. together with sutlicient C -C alkyl benzenes or similar aromatics such that the hydrocarbon mixture contains at least about 28 Weigt percent of aromatics. Up to '20 percent by weight of the entire solvent may consist of tetrahydrofuriuryl alcohol. This compound which behaves as a solubil-izing agent is beneficial indetergent compositions; and, therefore, in a preferred composition, the-solvent consists of approxirrlately 80 weight percent of aC -C alkylated benzene having an average of about 12 carbon atoms in the alkyl group and about 20 weight percent tetrahydrofurfuryl alcohol.

in another preferred composition, the solvent consists of from about 40 weight percent to weight percent of a petroleum distillate fraction boiling between about 300 F. and 600 F. (approximately 48 percent parafiins, 34 percent cycloparafiins, and at least 18 percent aromatics all by weight), from about 40 weight percent to weight percent of the described C -C alkyl benzeneand about weight percent tetrahydrofurfuryl alcohol.

In a particularly preferred composition, the mixture of surface-active agents ranges between SO'and 55 weight similar compositions prepared by blending the sodium salt of the same C -C alkyl benzene sulfonic acid also in the form of a 60 percent aqueous solution with the condensation products of octyl phenol with 1, 3, and 5 moles of ethylene oxide and with various combinations of solvents. The various compositions are set forth in Table I, and the appearance and properties of the resulting compositions are also shown.

Table 1 Composition numbe A-2 N-l N-3 N-5 Composition properties glear-Mfitv. ryst. pp Cryst. ppt. Cryst. ppt. Cryst. ppt. Cryst. ppt. Egeparated.

e Separated.

s s s s s s s s s wwwwwwwm .A1= Triethanolamine C -C alkyl benzene sulfonate,'60 weight percent aqueous solution (Ultrawet 60L).

A-2=So(lium Clo-C1 alkyl benzene sulionate, 60 weight percent aqueous solution.

1 mole octyl phenol condensed with 1 mole of ethylene oxide (Triton X-15) N -1 mole octyl phenol condensed with 3 moles of ethylene oxide (Triton X-). N-5=1 mole octyl phenol condensed with 5 moles of ethylene oxide (Triton X-).

S1=Petrolcum distillate fraction boiling between 300 F. and 600 F. containing 48 percent paraifins, 34 percent eycloparallins and 18 percent aromatics, by weight.

S2= 010-01 alkyl benzene.

(Boiling range 515" F.-590 F.)

8-3: Tetrahydrofurfuryl alcohol.

Clear=Forms clear solution.

M .W. ==Miscible with from 1 volume to 4 volumes of water. Cryst. ppt. =Crystals precipitated from the mixture. Separated=The mixture separated into two phases. Gel=The mixture formed ngel; components not miscible.

percent of the composition with the quantity of anionic surface-active agent and nonionic surface-active agent being approximately equal in par-ts by weight in the 'mixture and the solvent consists of from about 80 weight percent to 100 weight percent C -C alkyl benzene having an average of 12 carbon atoms in the alkyl group and from about 20 weight percent to 0 weight percent of tetrahydrofurfuryl alcohol.

The following examples are provided to illustrate the types of components and quantities of components suitable for use in this invention.

EXAMPLE I A composition was prepared by blending the triethanol- These results show that the sodium salt of the C -C alkyl benzene sulfonate cannot'be utilized in the compositions of this invention since the required clear, homogeneous solutions are not obtained, although various proportions of the sodium salt as well as various nonionic and solvent combinations with the sodium salt were tried.

EXAMPLE II Various compositions were prepared utilizing the triethanolamine salt of the C -C alkyl benzene sulfonic acid utilized in Example I admixed with the condensation products of octyl phenol with various quantities of ethylene oxide. The properties of these compositions are shown in Table II.

A-l, N-l, N-5, 8-1, 8-2, 8-3 and MW. are the same as in Example I.

N-7 =1 mole octyl phenol condensed with 7-8 moles of ethylene oxide (Triton X-114). N-9=1 mole octyl phenol condensed with 9-10 moles of ethylene oxide (Triton X-100). LW. =Immiseible with from 1 to 4 volumes of water.

amine salt of the C -C alkyl benzene sulfonic acid having an average of about 12 carbon atoms in the alkyl group in the form of a percent aqueous solution with an equal quantity by weight of a condensation product of 1 mole of octyl phenol with 5 moles of ethylene oxide utilizing a solvent consisting of 80 weight percent C -C alkyl benzene having an average of about 12 carbon atoms in the alkyl group and 20 weight percent tetrahydrofurfuryl alcohol.

These results show that only the condensation product of one mole of octyl phenol with 5 moles of ethylene oxide can be utilized to produce the compositions of this invention.

EXAMPLE III In order to show the solvents which may be utilized with the mixture of anionic surface-active agent and nonionic surface-active agent, a number of compositions were prepared whereinthe solvents were varied. The proper- This composition was utilized for comparison with ties of these compositions are shown in Table III.

A-l, N-5, S1, 8-2, 8-3 and MW. are the Siemens in Example I.

Results obtained in these experiments show that the solvent may range from 40 weight percent to 70 weight percent of a hydrocarbon fraction having an aromatic content of at least 28 weight percent, from about 40 Weight percent to weight percent of a C -C alkyl benzene and weight percent tetrahydrofurfuryl alcohol (Compositions Nos. 19, 20, and 2 1). It will also be seen by comparing Compositions Nos. 21 and 22 that the aromatic content of the solvent must be at least 28 weight percent. The results obtained from Compositions Nos. 1 and 1a show that the solvent may consist offrom about 80 weight percent to 100 weight percent C C alkyl benzene and from about 20 weight percent to 0 weight percent tetra :hydrofurf-uryl alcohol. Composition Nos. 23 to 26 show that it is not possible to utilize solvents outside of the desired ranges by varying the proportions of the anionic and nonionic surface-active agents.

EXAMPLE IV Compositions were prepared varying both the quantity of the mixture of anionic surface-active agent and nonionic surface-active agent as well as the proportions of the anionic and nonionic surface-active agents. The properties of these compositions are shown in Table IV.

Table IV Composition A-l N-5 S-2 S-3 Composition number properties 26. 7 26. 7 37. 2 9. 4 Clear-MW. 13. 3 40. 1 37. 2 9. 4 Separated. 40. l 13. 3 37. 2 9. 4 Do. 32.0 21. 4 37.2 9. 4 Do. 21. 4 32.0 37. 2 9. 4 Clear-MW. 13. 4 13. 4 63. 8 9. 4 Separated. 20. 0 20. 0 50. 5 9. 4 D0. 20. 0 20.0 47. 9 12. 1 D0. 23. 0 23. 0 43. 1 10. 9 Clear-1W. 40. 1 40. l 15. 8 4. 0 Do. 32.0 48. 0 20.0 Do. 30.0 30. 0 32. 0 8. 0 Clear-ltLW. 32. 5 32. 5 28. 0 7.0 Clear-LW.

A-l, N-5, 8-2, 8-3, M.W. and I.W. are same as in Examples I and II.

It is apparent from these experiments that the both proportions of anionic surface-active agent to nonionic surface-active agent and the total quantity of .the mixture are rather critical. The results show that the mixture of surface-active agents forms clear, water-soluble solutions when it amounts to from about 50 weight percent to 60 weight percent of the composition with the anionic surfaceactive agent ranging from 40 weight percent to 50 weight percent and the non-ionic surface-active agent ranging from 50 weight percent to 60 weight per-cent of the mixture of surface-active agents.

EXAMPLE V Certain of the preferred compositions were tested for removal of oil and oily products from the hands. About 2 cos. of used motor oil were utilized to soil the hands by rubbing the oil into the surface of the hands of the tester and then from about /2 to 1 cc. of the concentrated detergent composition was rubbed into the soiled portion 0.125 percent solids concentration.

of the hands. The hands were then rinsed under tap water. Utilizing the preferred Compositions Nos. 1, 1a, and 21, the hands were cleaned completely by this procedure, showing that the concentrate may be used as a liquid hand cleanser; for example, of the type used in liquid dispensers.

EXAMPLE VI The compositions were tested for their hard-surface detergencies. utilizing the method described by Jay C. Harris et al. entitled, Evaluation of Linoleum and Paint Cleanersfi in Soap and Sanitary Chemicals (July 1950). Trisodiurn phosphate was utilized as a standard at the It was arbitrarily rated at 100 percent for comparison purposes in order to determine cleaning efficiencies. The compositions of this invention were tested at the 0.25 percent level on the basis of the concentrate corresponding to a concentration of 0.08 percent of the active amount of surface-active agents. Composition No. 1 at this level gave an 80 percent efiiciency in cleaning and Composition No. It: gave an 87 percent efiiciency. Other compositions of the invention which were tested at this concentration also were within this range. Commercial products of this type, when tested at the 0.15 weight percent active level, gave eiiiciencies of the order of -60 percent which demonstrates that the instant compositions have excellent hard surface detergencies and are useful for cleaning painted floors, woodwork, walls, and the like.

ing essentially of from about weight percent to Weight percent of a mixture of an anionic surface-active agent and a nonionic surface-active agent, the remainder of the composition consisting of a solvent for said mixture of surface-active agents, said mixture of surface-active agents consisting of from about 40 weight percent to 50 weight percent of an aqueous solution of triethanolamine C -C alkyl benzene sulfonate of about 60 Weight percent concentration and from about 50 weight percent to 60' weight percent of the condensation product of one mole of octyl phenol with 5 moles of ethylene oxide, said solvent consisting of from about weight percent to weight percent of hydrocarbons boiling in the range of F. to 600 F., having a total aromatic content of at least about 28 weight percent and from about 20 weight percent to 0 weight percent of tetrahydrofurfuryl alcohol.

2. The composition according to claim 1 wherein the quantities of the anionic surface-active agent and the nonionic surface-active agent are about equal in parts by weight.

3. A water-soluble liquid detergent composition consisting essentially of from about 50 weight percent to 60 weight percent of a mixture of an anionic surface-active agent and a nonionic surface-active agent, the remainder of the composition consisting of a solvent for said mixture of surface-active agents, said mixture of surfaceactive agents consisting of from about 40 weight percent to 50 weight percent of an aqueous solution of triethanolamine C -C alkyl benzene sulfonate of about 60 weight percent concentration and from about 50 Weight percent to 60 weight percent of the condensation product of one mole of octyl phenol with 5 moles of ethylene oxide, said solvent consisting of from about 40 weight percent to 70 weight percent of a petroleum distillate fraction boiling between about 300 F. and 600 F. having an aromatic content of at least 18 percent by weight, from about 40 weight percent to 10 weight percent of C -C alkyl benzene and about 20 weight percent tetrahydroturfuryl alcohol.

4. The composition according to claim 3 wherein the quantities of anionic surface-active agent and the nonionic surface-active agent are about equal in parts by weight.

5. A water-soluble liquid detergent composition consisting essentially of from about 50 weight percent to 60 weight percent of a mixture of an anionic surface-active agent and a nonionic surface-active agent, the remainder of the composition consisting of a solvent for said mixture of surface-active agents, said mixture of surface-active agents consisting of from about Weight percent to weight percent of an aqueous solution of triethanolarnine C 'C alkyl benzene sulfonate of about weight percent concentration and from about 50 Weight percent to 60 weight percent of the condensation product of one mole of octyl phenol with 5 moles of ethylene oxide, said solvent consisting of from about weight percent to weight percent C -C alkyl benzene and from 20 Weight percent to 0 Weight percent tetrahydrofurfuryl alcohol.

6. The composition according to claim 5 wherein the quantities of anionic surface-active agent and the nonionic surface-active agent are about equal in parts by 15 weight.

References Cited bythe Examiner UNITED STATES PATENTS 2,607,740 8/52 Vitale et a1 252153 2,946,721 7/60 Hyatt et a1 252-1-61 XR 3,012,969 12/61 Van deMinne et 'al 252-153 3,018,251 1/62 Mayhew et a1 252153 XR FOREIGN PATENTS 582,455 9/59 Canada. 759,877 10/ 56 Great Britain.

OTHER REFERENCES Industrial Solvents, Mellan, Reinhold Pub. Corp., NY. (1950), (2nd Edition) (pages 5234241.).

JULIUS -GREENWALD, Primary Examiner. 

1. A WATER-SOLUBLE LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 50 WEIGHT PERCENT TO 60 WEIGHT PERCENT OF A MIXTURE OF AN ANIONIC SURFACE-ACTIVE AGENT AND A NONIONIC SURFACE-ACTIVE AGENT, THE REMAINDER OF THE COMPOSITION CONSISTING OF A SOLVENT FOR SAID MIXTURE OF SURFACE-ACTIVE AGENTS, SAID MIXTURE OF SURFACE-ACTIVE AGENTS CONSISTING OF FROM ABOUT 40 WEIGHT PERCENT TO 50 WEIGHT PERCENT OF AN AQUEOUS SOLUTION OF TRIETHANOLAMINE C10-C16 ALKYL BENZENE SULFONATE OF ABOUT 60 WEIGHT PERCENT CONCENTRATION AND FROM ABOUT 50 WEIGHT PERCENT TO 60 WEIGHT PERCENT OF THE CONDENSATION PRODUCT OF ONE MOLE OF OCTYL PHENOL WITH 5 MOLES OF ETHYLENE OXIDE, SAID SOLVENT CONSISTING OF FROM ABOUT 80 WEIGHT PERCENT TO 100 WEIGHT PERCENT OF HYDROCARBONS BOILING IN THE RANGE OF 175*F. TO 600*F. HAVING A TOTAL AROMATIC CONTENT OF AT LEAST ABOUT 28 WEIGHT PERCENT AND FROM ABOUT 20 WEIGHT PERCENT TO 0 WEIGHT PERCENT OF TETRAHYDROFURFURYL ALCOHOL. 